Azo dyes derived from acylacetyl compounds of diamins and process of making same



Patented Aug. 19, 1924.

AUGUST LEOPOLD LASKA AND ARTHUR ZI'ISGHER, OF OFFENBACH-ON-THE -MAIN,

GERMANY, ASSIGNORS TO THE CORPORATION CHEMISCHE FABRIK GRIESHEIM- ELEKTRON, 0F FRANKFORT-O NTHE-MAIN, GERMANY.

AZO DYES DERIVED FROM AGYLAGETYL COMPOUNDS OF DIAMINS AND PROCESS OF MAKING-SAME No Drawing.

To all whom it may concern:

Be it known that we, AUGUST LEOPOLD LASKA and ARTHUR ZITSCHER, both citizens of the German Republic, and residents of Offenbach-on-the-Main, Germany, have invented certain new and useful Improvements in azo dyes derived from acylacetyl c0mp0l1nds of diamins and processes of making same; and we do hereby declare the following to be'a full, clear, and exact de scription of the invention, such as will enable others skilled in the art to which it appertains to make and use the same.

Our invention relates to new azo dyestuffs, which can be used for the production of pigment colors and which can be also produced on the vegetable fibre.

We have found, that by combining a Application filed November 23, 1922. Serial No. 602,896.

diazo compound not containing a sulfo or carboxylic group with a diacylacetyl compound of t e general formula:

and the like.

The new dyestuffs are when dry yellow to brown and Bordeaux red powders, in-

. soluble in water and soluble in sulfuric acid to a yellow to violet solution, they can be used for the production of valuable pigment colors and give, when produced on the fiber, shades of a complete fastness to washing and of an excellent fastness'to chlorine.

As diazo compounds those of aniline and its homologues and substitution products, such as toluidine, anisidine, chloroand nitroanilines, chloroand nitrotoluidines, chloroand nitroanisidines, also those of naphthylamines, aminoanthraquinones, aminoazo compounds, diamino bases and others are available for the process, as azocomponents we may use for example the diacylacetyl compounds from thioaniline, diaminodiphenylether, diaminodiphenylmethane, diamininobenzophenone, diaminoazobenzene, diaminoazoxybenzene, diaminodiphenylamine, diaminodiphen lurea, aminobenzoylphenylenediamine an so on, which can be obtained by condensing acylacetic acid esters with the corresponding bases.

The following examples illustrate the invention, the parts being by weight.

Example 1.

PRODUCTION or THE Dmsrorrs ON FIBER Example 2.

The yarn, having been well boiled and dried, 1s impregnated with a solution of 10 gr. of diacetoacetyl-4.4'-diaminoazoxybenzene 15 cc. of caustic soda lye of 34 B. and

20 cc. of Turkey red oil in the liter, well wrung out and without being dried, developed in a diazo solution, with an addition of sodium acetate and containing 2.6 gr. of ortho-chloroanilii1e in the liter.

In this manner clear, reddish yellow tints of a very good fastness are obtained.

Example 3. The yarn, having been well boiled and dried, is impregnated with a solution of gr. of di-acetoacetyliA-diaminoazobenzene cc. of caustic soda lye of 3 B. and cc. of Turkey red oil in the liter, well wrung out and without being dried, developed in a diazo solution with an addition of sodium acetate and containing 2.8;

gr. of orthonitroaniline in the liter.

In this manner reddish yellow tints of a ver good fastness are obtained.

he new dyestufi's can also be produced by printing a diazo solution upon a padded fabric according to the usual method, also according to the method of nitrosamine rinting.

With other diazo compounds and other corresponding di-acetyl compounds of diamino bases, the process may be conducted similarly.

The following table gives some of the shades of .a number of the dyestuffs, prepared according to the present process and of the color lakes, respectively, obtained therefrom:

Diazo compound from- Combined with- Shades 5-Nitro-l.2 toluidine.. Di-acetoacetyl-4.4'- Yellow.

diamino-benzophenone. 6-Nitro-1.2-toluidine. D1-acetoacetyl-4.4'- Greenish yellow. diamino-3.3'-ditw lylmethane.

Amlme Reddish yellow.

Di-acetoacetyl-4.4- diamino azoben- Ortho-chloroaniline Do. 2.5-Dichloroaniline- Do. 5-Ch1oro-1.2-toluidine Do. 5-Nitro-L2-toluidine Yellow orange. e-N tro-l-naphthyla- Yellow brown.

mine. u-Aminoanthraquinone Browmsh orange.

Golden orange. Cupreous brown.

Ortho-aminoazotoluene Ortho-anisol-azo-naphthylamine Now what we claim and desire to secure by Letters Patent is the following:

1. As new products the azodyestufl's, in soluble' in water, which can be obtained by combining a diazocompound not containing a sulfo or carboxylic group with a diacylacetyl compound of the general formula:

Y.CO.GH .CO.NH.R.X.

' RNH.CO.CH .CO.Y,

wherein R and R represent aryl residues, X a connecting link and Y any radical of the hydrocarbon series, which dyestuffs probably have the general formula:

HN=-Naryi do i, wherein R and R represent aryl residues, X a connecting link and Y any radical of the hydrocarbon series, which are when dry yellow to brown and Bordeaux red powders,

insoluble in water, and soluble in sulfuric acid to a yellow to violet solution, which dyestufl's yielding valuable lakes and, when produced on the fiber, fast yellow to brown and Bordeaux red shades.

2. A process of making azodyestufl's, insoluble in water consisting in combining a diazo compound not containing a sulfo or carboxylic group with a diacylacetyl compound of the general formula:

rooon oonnnx. R.NH.GO.CH2.GO.Y,

wherein R an R represent aryl residues, X

a connecting link and Y any radical of the hydrocarbon series.

3. A. processof producing on the fiber of cotton goods azodyestufi's insoluble in water, which-consists in treating the cotton goods after impregnation with a diacylacetyl compound of the general formula vooon cornnx. 'R'.NH.GO.CH2.CO .Y,

wherein R and R represent aryl residues, X a connecting link and Y any radical of the hydrocarbon series, pound not containinga P- Q V with a diazo comsulfo or carboxylic 4. As new products the azodyestufl's, insoluble in water, which can be obtained by combining a diazocompound not containing a sulfo or carboxylic group with a diaceto acetyl compound of the general formula:

wherein R and R represent aryl residues and X a connecting link, which dyestuffs probably have the general formula:

0 dH N- N-aryl CH,.CO.CH2.CO.NH.R.X.

R'.NH.oo.cH,.oo.oH,, v

wherein R and R represent aryl residues and X a connecting link.

6. A process of producing on the fiber of cotton goods, azodyestuifs insoluble in water, which consists in treating the cotton goods after impregnation with a diacetoacetyl compound of the general formula:

wherein R and R represent aryl residues and X a connecting link, with a diazo compound not containing a sulfo or carboxylic group.

7. As new articles the azodyestufi's, insoluble in water, which can be obtained by combining a diazo compound negatively sub= yellow to brown stituted and not containing a sulfo or carboxylic group, with a diacetoacetyl compound of the general formula:

CH,.CO.CH .CO.NH.R.X.

R.NH.OO.CH .GO.CH

wherein R and R represent aryl residues and X a connecting link, which dyestufl's probably have the general formula:

HN-=N--ary1 (negatively substituted) J; 1i tH a H-N=Naryl (negatively substituted) wherein R and R' represent aryl residues and X a connecting link, which are when dry yellow to brown and Bordeaux red powders, insoluble in water, and soluble in sulfuric acid to a yellow to violet solution, said dyestuffs yielding valuable lakes and, when produced on the fiber, fast yellow to brown and Bordeaux red shades.

8. A process of making azodyestufi's, insoluble in water consisting in combining a diazo compoundnegatively substituted and not containing a sulfo or carboxylic group, with a diacetoacetyl compound of the general formula:

wherein R and R represent aryl residues and'X a connecting link.

9. A processof producing on the fiber of cotton goods, azodyestuffs insoluble in water, which consists in treatin the cotton goods after impregnation wit% a diacetoacetyl compound of the general formula:

GH3.CO.CH2.CO.NH.R.

X.R'.NH.co.oH,.oo.oH,,

wherein R and R represent aryl residues and X a connecting link, with a diazo compound negatively substituted and not containing a sulfo or carboxylic-group.

10. As new articles the azodyestufi's, insoluble in water, which can be obtained by combining a diazo compound not containing a sulfo or carboxylic group with diacetoacetyldiaminoazobenzene, which dyestufi's proba ly have the general formula:

(iH-N-N-aryl which are when dr yellow to brown and Bordeaux red pow ers, insoluble in water, and soluble in sulfuric acid to a yellow to violet solution, said dyestufl's yielding valuazobenzene.

12..A process of producing on the fiber of cotton goods, azodyestuffs insoluble in water, which consists in treating the cotton goods, after impregnation with dia-cetoacetyldiaminoazobenzene, with a diazo compound not containing a sulfo or carboxylic group.

13. As new articles the azodyestufi's, insoluble in water, which-can be obtained by combining a diazo compound negatively substituted and not containing a sulfo or carboxylic group, with diace'toacetyldiaminoazoof cotton goods,

benzene, which dyestuffs probably have the general formula:

H--N-Neryl (negatively substituted) H: which are, when dry, yellow to brown and Bordeaux red powders insoluble in water, and soluble in sulfuric acid to a yellow to violet solution, said dyestuffs yielding valuable lakes and when produced on the fiber, fast yellow to brown and Bordeaux red shades. p

14. A process of'making azodyestuffs, insoluble in water consisting in combining a diazocompound negatively substituted and not containing a sulfo or carboxylic group, with diacetoacetyldiaminoazobenzene.

15. A process of producing on the fiber azodyestuffs insoluble in water, which consists in treating the cotton goods, after impregnation with diacetoacetyldiaminoazobenzene. with a diazocompound negatively substituted and not containing a sulfo or'carboxylic group.

In testimony whereof we afiix our signatures.

AUGUST LEOPOLD LASKA. ARTHUR ZITSCHER.

Witnesses:

C. C. S. B. WYLES, F. A. Wnmmms. 

